US20090244810A1 - Electrochemical capacitor - Google Patents
Electrochemical capacitor Download PDFInfo
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- US20090244810A1 US20090244810A1 US12/058,772 US5877208A US2009244810A1 US 20090244810 A1 US20090244810 A1 US 20090244810A1 US 5877208 A US5877208 A US 5877208A US 2009244810 A1 US2009244810 A1 US 2009244810A1
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- 239000003990 capacitor Substances 0.000 title claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 67
- 239000011230 binding agent Substances 0.000 claims abstract description 37
- 239000011263 electroactive material Substances 0.000 claims abstract description 36
- 239000002105 nanoparticle Substances 0.000 claims abstract description 21
- 239000002800 charge carrier Substances 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 78
- 239000002131 composite material Substances 0.000 claims description 69
- 239000002077 nanosphere Substances 0.000 claims description 44
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 37
- 239000005083 Zinc sulfide Substances 0.000 claims description 36
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 36
- 239000003792 electrolyte Substances 0.000 claims description 22
- 150000002500 ions Chemical class 0.000 claims description 20
- 239000012528 membrane Substances 0.000 claims description 10
- 229910001385 heavy metal Inorganic materials 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 45
- 239000000370 acceptor Substances 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 45
- 239000002086 nanomaterial Substances 0.000 description 27
- 229940063789 zinc sulfide Drugs 0.000 description 27
- 238000000197 pyrolysis Methods 0.000 description 23
- 241000894007 species Species 0.000 description 21
- 238000000034 method Methods 0.000 description 18
- 230000008569 process Effects 0.000 description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
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- 238000004519 manufacturing process Methods 0.000 description 12
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- 239000003575 carbonaceous material Substances 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052976 metal sulfide Inorganic materials 0.000 description 5
- 125000006850 spacer group Chemical group 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- -1 carbon fullerenes Chemical class 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- 239000004020 conductor Substances 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
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- 239000011787 zinc oxide Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
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- 239000011651 chromium Substances 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
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- 239000011734 sodium Substances 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000372132 Hydrometridae Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910021387 carbon allotrope Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007723 transport mechanism Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/42—Powders or particles, e.g. composition thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention relates to electrodes and electrochemical devices having electrodes that undergo electrochemical reactions and particularly to nanomaterial electrodes and devices.
- Nanomaterials are materials that include components with nanometer dimensions, for example, where at least one dimension is less than 100 nanometers. Examples of such materials are allotropes of carbon such as nanotubes or other carbon fullerenes and components of carbon char. Carbon black was an early use of nanomaterials in tire manufacturing. Other nanomaterials include inorganic materials such as metal sulfides, metal oxides and organic materials. Because of the small dimensions, nanomaterials often exhibit unique electrical and electrochemical properties and unique energy transport properties. These properties are most pronounced when high surface areas are present and when charge transport mechanisms exist in the nanomaterials.
- Nanomaterials are manufactured using rigorous processing steps that are expensive and commercially unattractive. Some nanomaterials occur naturally or incidentally in commercial processing steps. Naturally or incidentally occurring nanomaterials tend to be highly irregular in size and composition because the environment in which they are produced is not adequately controlled for the production of nanomaterials. Processing methods that produce nanomaterials include among others, liquid-phase steps, gas-phase steps, grinding steps, size-reduction steps and pyrolysis steps.
- Pyrolysis is the heating of materials in the absence of oxygen to break down complex matter into simpler molecules and components.
- carbon based materials are pyrolyzed, the process of carbonization can occur leading to an ordered state of semi-graphitic material.
- carbon based materials are pyrolyzed in uncontrolled conditions, a large amount of randomly ordered carbon material results.
- pyrolysis under controlled conditions can lead to highly useful and unique results.
- An example of a use of pyrolysis is for the break down of used tires (typically from automobiles, trucks and other vehicles). The pyrolysis of tires results in, among other things, a carbon/inorganic residue called char.
- the composition of char from tire pyrolysis is determined by the materials that are used to manufacture tires.
- the principal materials used to manufacture tires include rubber (natural and synthetic), carbon black (to give strength and abrasion resistance), sulfur (to cross-link the rubber molecules in a heating process known as vulcanization), accelerator metal oxides (to speed up vulcanization), activation inorganic oxides (principally zinc oxide, to assist the vulcanization), antioxidant oxides (to prevent sidewall cracking), a textile fabric (to reinforce the carcass of the tire) and steel belts for strength.
- the carbon black has a number of carbon structures including graphitic spheroids with nanometer dimensions, semi graphitic particles and other forms of ordered carbon structures.
- the manufacture of tires initially mixes the materials to form a “green” tire where the carbons and oxides form a homogenous mixture.
- the “green” tire is transformed into a finished tire by the curing process (vulcanization) where heat and pressure are applied to the “green” tire for a prescribed “cure” time.
- the carbon materials used in “green” tires are typically as indicated in TABLE 1:
- tire pyrolysis involves the thermal degradation of the tires in the absence of oxygen.
- Tire pyrolysis has been used to convert tires into value-added products such as pyrolytic gas (pyro-gas), oils, char and steel. Pyrolysis is performed with low emissions and other steps that do not have an adverse impact on the environment.
- the basic pyrolysis process involves the heating of tires in the absence of oxygen. To enhance value, the oils and char typically under go additional processes to provide improved products.
- electrochemical capacitors electrical charge is stored on the surface of an electrically conductive electrode material.
- the capacitance arises by separation of electrons at the electrode surface and ionic charges in the electrolyte solution. Because the charge separation arises over only a distance of 0.1 to 10 nanometers, large specific capacitances can be achieved on the order of 10-20 microfarads per square centimeter of electrode material. The larger the surface area of the electrode material, the greater the charge that can be stored. Since the capacitance, or the amount of charge that an electrochemical capacitor can hold, is directly related to the surface area of the electrodes, electrodes made from conductive materials with high surface areas are preferred. Devices incorporating such electrodes are referred to as double layer capacitors or supercapacitors.
- Electrochemical capacitors are charge-storage devices that are capable of delivering high power densities and that are capable of being cycled (charged and discharged) millions of times, hence demonstrating a significant advantage over conventional batteries. Electrochemical capacitors have energy and power capabilities that lie between the capabilities of a battery and of a conventional capacitor (electrolytic, thin film and others).
- Double layer capacitors are rechargeable charge storage devices that fulfill this need.
- activated carbon is an energy intensive process that first includes heating of a precursor material (natural or synthetic) to form a carbon powder or carbon fiber, in many cases requiring temperatures up to 3000° C.
- a precursor material naturally or synthetic
- the material is heated to about 800° C. in an atmosphere of steam or carbon dioxide, or electrochemical reaction in a strongly oxidizing solutions (such as Hummers reagent) to produce a carbon with high surface area to provide high energy density and high power density.
- a strongly oxidizing solutions such as Hummers reagent
- a single cell double-layer capacitor consists of two electrodes which store electrical charge (called the active materials), separated by an ion permeable but electrically insulating membrane. Each electrode is also in contact with a current collector which provides for electrical contact outside of the cell.
- the electrodes and membrane are infused with an electrolyte and enclosed in an inert housing which provides a sealed environment and also enough compression to reduce contact resistance between the different layers.
- Multiple cells may be used in series to increase the allowable potential (voltage), and also in parallel to increase the capacitance.
- the desired properties of the electrochemical capacitor electrodes include the following high surface area, electrically conductive, low cost, readily available source of material and long-term stability under operating conditions.
- the present invention is an electroactive material for charge storage and transport in an electrochemical capacitor.
- the material is formed of a plurality of nanocomponents including nanoparticles, in turn formed of conductive carbon-based clusters bound together by a conductive carbon-based cluster binder including zinc sulfide nanoclusters and nanocluster binders, all having high densities of mobile charge carriers (electrons, electronic acceptors, ionic species).
- a terminal is electrically coupled to the nanoparticles for charge transport.
- the material and each of the nanocomponents play key roles in the process of charge transport including supplying electrons and electron acceptor sites.
- the charge transport occurs by the electron travel through the highly conductive and relatively short path of the binders with proximity to the nanoclusters.
- the small sizes of the particles provide large surface areas. In general, particle sizes of less than about 100 nanometers are preferred in order to have large surface areas which provide ready access of the electrolyte to the nanocomponents of the particles.
- the combination of the high density of available electrons in all the nanocomponents of the particles with the short distances among all the nanocomponents of the particles and the large surface areas of the nanocomponents greatly enhances the energy and power densities achieved.
- a second electroactive material is provided for charge transport.
- the second material is formed of a second plurality of nanocomponents including second nanoparticles, in turn formed of conductive carbon-based clusters bound together by a conductive carbon-based cluster binder including nanoclusters and nanocluster binders, all having high densities of mobile charge carriers (electrons, electronic acceptors, ionic species).
- a second terminal is electrically coupled to the nanoparticles for charge transport.
- the second plurality of particles are substantially the same as the first plurality of particles including zinc sulfide nanoclusters.
- the second plurality of particles are substantially different from the first plurality of particles including zinc sulfide nanoclusters.
- the zinc sulfide nanoclusters are charge receptors and wherein charge transport uses electrolyte ions.
- the second plurality of particles are separated from the first plurality of particles by an ion permeable membrane.
- the carbon nanosphere cores have diameters of less than approximately 100 nanometers.
- the electroactive material of claim 2 wherein the composite layer has a wall thickness of less than approximately 1200 nanometers.
- a substantial number of the clusters have diameters of less than approximately 1200 nanometers.
- FIG. 1 is a schematic representation of material formed of particles including composites having nanoclusters.
- FIG. 2 depicts a schematic representation of a typical particle of the FIG. 1 material including composites having nanoclusters.
- FIG. 3 depicts a schematic representation of a typical composite having zinc sulfide nanoclusters.
- FIG. 4 depicts a schematic representation of a typical composite having zinc nanoclusters.
- FIG. 5 depicts an electroactive material having nanoparticles and having a terminal electrically coupled to the particles for charge transport.
- FIG. 6 depicts a device including first and second electroactive materials of the FIG. 5 type, each having nanoparticles and having a terminal electrically coupled to the particles for charge transport.
- FIG. 7 depicts a device including a first electroactive material including a second electroactive material, different from the first electroactive material, having nanoparticles and having a terminal electrically coupled to the particles for charge transport.
- FIG. 8 depicts a device including first and second electroactive materials and including a third electroactive material, like the first electroactive material and having nanoparticles and having a terminal electrically coupled to the particles for charge transport.
- FIG. 9 depicts a schematic expanded representation of an electrochemical capacitor having one electrode formed of particles including composites having zinc sulfide nanoclusters (anode) and another electrode formed of particles including composites having zinc sulfide nanoclusters (cathode).
- FIG. 10 depicts a schematic expanded representation of a electrochemical capacitor of the FIG. 9 type having added spacers
- FIG. 11 depicts a schematic collapsed representation of the electrochemical capacitor of the FIG. 10 .
- FIG. 12 depicts a representation of an anode and cathode formed of electroactive materials.
- FIG. 13 depicts an electron-microscope scan of a particle including composites having zinc sulfide nanoclusters.
- FIG. 14 depicts an electron-microscope scan of one of the nanoclusters of FIG. 13 .
- FIG. 15 depicts an electron-microscope scan showing further details of the nanocluster of FIG. 14 .
- FIG. 16 depicts an electron-microscope scan showing even further details of the nanocluster of FIG. 15 .
- the electrode materials used in electrochemical capacitors serve multiple concurrent functions by acting both as a battery and an electrochemical capacitor with tunable power and energy capabilities.
- the cost of the carbon-based electrode materials is substantially reduced through use of materials derived from tire pyrolysis.
- These nanosized carbon-based materials are preferred materials for the electrodes in electrochemical capacitors due to their large surface areas and high charge densities.
- the large surface areas and high charge densities are accessible to the charge carrying electrolyte ions. Highly accessible surface areas and high charge densities are important for high energy density and high power density.
- the char obtained from the pyrolysis of tires is an inexpensive source of nanomaterials that, with further control and added processing, are potentially useful in many fields including Photo Catalysts, Contact Catalysts, Capacitors, Batteries, Sorbents (Adsorbents and Absorbents) and Photo Voltaic Materials.
- the ability to use nanomaterials derived from char in useful applications is dependent on controlling the parameters of the tire pyrolysis process and the processing of char for particular applications.
- Typical electrolytes include aqueous, organic, inorganic and polymeric.
- the electron transfer can occur at an electrode through the release of chemical energy to create an internal voltage or through the application of an external voltage.
- Electrochemical reactions transfer electrons between atoms or molecules. These reactions can be separated in space and time and devices with such reactions are often connected to external electric circuits. The creation of internal voltages at electrodes is useful in electrochemical capacitors.
- One example of batch pyrolysis uses a furnace/retort, a three stage condensing system, a water scrubber, and a flare.
- An oil tank collects the condensed oil at the end of each test.
- the furnace uses two burners.
- the operating temperature of the furnace is set at 1,750° F. with a control range of plus/minus 30 to 40° F.
- the control temperature is reached, one burner is shut off continuing with a small upward drift in temperature.
- the burner restarts automatically. Both burners are on for the first 90 minutes. Burner cycle time after the start of the run is a few seconds; near the end of the run, one burner is off for period as long as three minutes with a like interval of being on.
- Exhaust gas temperature remains relatively stable between 1,250 and 1380° F. Pyro gas generation starts after 105 minutes of operation at a temperature of 650° F., reached a high of 700° F., and dropped to 375° F. at the end of the thermal cycle.
- the control of the temperatures and the control of the heating and cooling rates during pyrolysis are critical for producing the nanocomponents having the nano structures of the present invention.
- the thermal operation is monitored using the back pressure in the retort, the cooling water temperature, and visually watching the flare.
- a run lasts approximately 16 hours. At the end of the run, the furnace back pressure is almost atmospheric, the cooling water delta temperature is almost zero, and the flare is out. During this operational period, the ambient air temperature ranged from about 20 to 45° F.
- the retort is opened approximately 8 hours after the thermal cycle is shut down. The estimated temperature of the char is less than 350° F. Prior to opening the retort, the retort is purged with nitrogen for a brief period of time. After the lid is opened, a very small quantity of vapor comes from the remaining char and tire wire.
- Cooling water flow (rate and temperature) is monitored as a check of the process gas generation rate and the condensing duty for both the condensable and non-condensable fraction of the process gas produced.
- the operating pressure of the retort ranges from two to eight millibars above atmospheric, which is sufficient to transport the gas through the condensing system to the flare.
- the tire charge was 3,400 pounds in eight bales.
- the eight bales averaged 15 tires, with an average weight of 28 pounds per tire.
- the output yield of char was approximately 25% or more of the tire input.
- the composition of char includes carbon as previously indicated in TABLE 1 and includes inorganic materials, such as metal sulfides and metal oxides, as indicated in the following TABLE 2:
- TABLE 1 materials and TABLE 2 materials as produced by the pyrolysis process form nanomaterial composites useful in many fields including Photo Catalysts, Contact Catalysts, Capacitors, Batteries, Sorbents (Adsorbents and Absorbents) and Photo Voltaic Materials.
- the TABLE 2 materials are “heavy metal free” in that even if trace amounts of heavy metals were produced as a result of tire pyrolysis, the trace amounts are so small that no environmental hazard is presented.
- the material 5 includes nanomaterial in the form of particles 21 derived from char in the manner previously described.
- the char is processed for size reduction, sorting, classification and other attributes to form the char particles 21 .
- FIG. 2 a schematic representation of a particle 21 is shown that is typical of the particles 21 in the material 5 of FIG. 1 .
- the particles 21 of FIG. 1 typically have at least one dimension, P, in a range from approximately 10 nm to approximately 10,000 nm.
- the particle 21 includes a plurality of clusters 30 that are held together by a cluster binder 22 .
- the material of the cluster binder 22 primarily contains components of TABLE 1 and TABLE 2.
- a number of the clusters 30 are externally located around the periphery of the particle 21 and a number of the clusters 30 , designated as clusters 30 ′, are located internally away from the periphery of particle 21 .
- the internally located clusters 30 ′ are loosely encased by the cluster binder material 22 .
- the selection of particle sizes in a range from approximately 50 nm to approximately 1000 nm tends to optimize the number of active and externally located clusters 30 and thereby enhances the electrochemical operations of the electrodes.
- the internally located clusters 30 ′ are efficiently coupled electrically and through intercalation.
- FIG. 3 a schematic representation is shown of a cluster 30 - 1 that is typical of one embodiment of clusters 30 of FIG. 2 .
- the cluster 30 - 1 has a graphitic carbon nanosphere cores 33 encased by a composite layer 34 .
- the carbon nanosphere core 33 is generally spherical in shape (a nanosphere) and has a core diameter, D C1 , in a range from approximately 10 nanometers to approximately 1000 nanometers.
- the composite layer 34 has a wall thickness, W T1 , in a range from approximately 0.2 nanometers to approximately 300 nanometers.
- the overall diameter of the cluster 30 - 1 (D C1 +W T1 ) in a range from approximately 10 nanometers to approximately 1300 nanometers.
- the size and shape of the carbon nanosphere cores 33 are limited primarily by the size and the shape of the cores used in the mixture forming the “green” tires as indicated in TABLE 1.
- the melting point of graphite is approximately in the range from 1900° C. to 2800° C. Since both the vulcanization and the pyrolysis processes operate at much lower temperatures, the carbon nanosphere cores 33 in finished tires and in tire char remain essentially undisturbed from their original size and shape.
- the composite layers 34 surrounds and incases the carbon nanosphere cores 33 .
- the sizes and the shapes of the composite layers 34 are determined in part by the sizes and the shapes of the carbon nanosphere cores 33 and additionally by the processing of the tire char.
- the processing of the char is done so as to achieve the 0.2 nanometers to approximately 300 nanometers for the wall thickness, W T1 , and so as to achieve the overall diameter, (D C1 +W T1 ), of the clusters 30 - 1 in a range from approximately 10 nanometers to approximately 1300 nanometers.
- the composite layer 34 is carbon and contains a mixture of metal oxides and metal sulfides of TABLE 2 and other materials as described in TABLE 1, surrounding and bound to the carbon nanosphere core 33 .
- the composite layer 34 includes zinc sulfide nanoclusters 32 embedded in and forming part of the composite layer 34 .
- a number of the nanoclusters 32 are externally located, that is, located around the periphery of the cluster 30 - 1 and a number of the nanoclusters 32 , designated as nanoclusters 32 ′, are located internally away from the periphery of the composite layer 34 .
- the composition of the composite layer 34 typically has zinc sulfide (ZnS) in a range, for example, of 2% to 20% by weight, and carbon and other components of TABLE 2.
- FIG. 4 a schematic representation is shown of a cluster 30 - 2 that is typical of one embodiment of clusters 30 of FIG. 2 .
- the cluster 30 - 2 has a carbon nanosphere core 43 encased by a composite layer 34 .
- the carbon nanosphere core 43 is generally spherical in shape (a nanosphere) and has a core diameter, D C2 , in a range from approximately 10 nanometers to approximately 1000 nanometers.
- the composite layer 34 has a wall thickness, W T2 , in a range from approximately 0.2 nanometers to approximately 300 nanometers.
- the overall diameter of the cluster 30 - 2 (D C2 +W T2 ) in a range from approximately 10 nanometers to approximately 1300 nanometers.
- the size and shape of the carbon nanosphere cores 43 are limited primarily by the size and the shape of the cores used in the mixture forming the “green” tires as indicated in TABLE 1.
- the melting point of graphite is approximately in the range from 1900° C. to 2800° C. Since both the vulcanization and the pyrolysis processes operate at much lower temperatures, the carbon nanosphere cores 43 in finished tires and in tire char remain essentially undisturbed from their original size and shape.
- the composite layers 34 surrounds and incases the carbon nanosphere cores 43 .
- the sizes and the shapes of the composite layers 34 are determined in part by the sizes and the shapes of the carbon nanosphere cores 43 and additionally by the processing of the tire char.
- the processing of the char is done so as to achieve the 0.25 nanometers to approximately 80 nanometers for the wall thickness, W T2 , and so as to achieve the overall diameter, (D C2 +W T2 ), of the clusters 30 - 2 in a range from approximately 5 nanometers to approximately 100 nanometers.
- the composite layer 34 is a mixture of metal oxides and metal sulfides of TABLE 2 and other materials as described in TABLE 1, surrounding and bound to the carbon nanosphere core 43 .
- the composite layer 34 includes zinc sulfide nanoclusters 32 embedded in and forming part of the composite layer 34 .
- a number of the nanoclusters 32 are externally located, that is, located around the periphery of the cluster 30 - 2 and a number of the nanoclusters 32 , designated as nanoclusters 32 ′, are located internally away from the periphery of the composite layer 34 .
- the composition of the composite layer 34 typically has zinc sulfide (ZnS) in a range from approximately 2% to approximately 20% by weight, carbon in a range from approximately 60% to approximately 70% by weight, with the balance of the composite layer 34 principally being a mixture of metal oxides and metal sulfides of TABLE 2 and other materials as described in TABLE 1.
- ZnS zinc sulfide
- FIG. 5 depicts an electroactive material 21 5 having nanoparticles and having a terminal 565 electrically coupled to the particles for charge transport.
- the terminal 565 functions as an electrode for allowing charge transport to and from the particles forming the nanomaterial 21 5 .
- FIG. 6 depicts a device including first and second electroactive materials 21 - 1 6 and 21 - 2 6 of the FIG. 5 type, each having nanoparticles and having terminals 56 - 1 6 and 56 - 2 6 electrically coupled to the particles of the first and second electroactive materials 21 - 1 6 and 21 - 2 6 , respectively, for charge transport.
- FIG. 7 depicts a device including a first electroactive material electroactive material 21 - 1 7 of the FIG. 5 type and having terminals 56 - 1 7 and including a second electroactive material 21 - 2 7 , different from the first electroactive material, having nanoparticles and having a terminal 56 - 2 7 electrically coupled to the particles for charge transport.
- FIG. 8 depicts a device a device including first and second electroactive materials 21 - 1 8 and 21 - 2 8 of the FIG. 5 type, each having nanoparticles and having terminals 56 - 1 8 and 56 - 2 8 electrically coupled to the particles of the first and second electroactive materials 21 - 1 8 and 21 - 2 8 , respectively, for charge transport and including a third electroactive material 21 - 3 8 , like the first electroactive material and having nanoparticles and having a terminal 56 - 3 8 electrically coupled to the particles for charge transport.
- FIG. 9 a schematic representation of an electrochemical capacitor 50 is shown having one electrode (anode) 52 and another electrode (cathode) 54 .
- the anode 52 is formed of particles 21 as described in connection with FIG. 1 , FIG. 2 and FIG. 3 and includes cluster 30 and specifically cluster 30 - 1 having zinc sulfide nanoclusters 32 .
- the cathode 54 is formed of particles 21 as described in connection with FIG. 1 , FIG. 2 and FIG. 3 and includes cluster 30 and specifically cluster 30 - 2 having zinc sulfide nanoclusters 32 .
- the electrode (anode) 52 and electrode (cathode) 54 are immersed in a solution 58 which in one example is 38% potassium hydroxide, KOH, in water.
- a separator 53 is provided between the anode 52 and the cathode 54 .
- the separator 53 is a membrane which pre-vents any carbon transfer or contact between the anode 52 and the cathode 54 while permitting the transport of electrolyte ions.
- the anode 52 contacts a metal or other good-conducting material 51 to enable electron flow at terminal 56 .
- the cathode 54 contacts a metal or other good-conducting terminal connector 55 to enable electron flow at contact 57 .
- the capacitor elements 51 , 52 , 53 , 54 and 55 are schematically shown with exaggerated spacing for clarity in the description and ease of viewing the drawing.
- FIG. 10 a schematic representation of capacitor 50 of FIG. 9 is shown having the addition of spacers 560 and 570 .
- the spacer 560 is between the anode 52 and the membrane separator 53 .
- the spacer 570 is between the cathode 54 and the membrane separator 53 .
- the spacers 560 and 570 help establish the thickness of the capacitor 50 and also provide hermetic seals that constrain the electrolyte 58 .
- the capacitor elements 51 , 52 , 53 , 54 , 55 , 560 and 570 are schematically shown with exaggerated spacing for clarity in the description and ease of viewing the drawing.
- FIG. 11 a schematic representation of capacitor 50 of FIG. 6 is shown without expanded spacing.
- FIG. 12 the capacitor 50 shown in FIG. 9 , FIG. 10 and FIG. 11 is shown with greater details of the nanoscale structure of the materials and of the charge transport.
- the capacitor 50 includes a first electroactive electrode 52 - 1 including a material 5 - 1 formed of plurality of particles 21 - 1 .
- Each includes a plurality of clusters, of which cluster 30 - 1 is typical.
- Each cluster includes a carbon nanosphere core 33 , a composite layer 34 surrounding and bound to the carbon nanosphere core 33 .
- the composite layer 34 includes zinc sulfide nanoclusters 32 embedded in the composite layer 34 , and a binding composite 31 binding the plurality of nanoclusters 32 .
- a first terminal 56 12-1 electrically couples to the first plurality of particles 21 - 1 for charge transport.
- a second electroactive electrode electroactive electrode 52 - 2 including a material 5 - 2 formed of plurality of particles 21 - 2 .
- Each includes a plurality of clusters, of which cluster 30 - 2 is typical.
- Each cluster includes a carbon nanosphere core 33 , a composite layer 34 surrounding and bound to the carbon nanosphere core 33 .
- the composite layer 34 includes zinc sulfide nanoclusters 32 embedded in the composite layer 34 , and a binding composite 41 binding the plurality of nanoclusters 32 .
- a second terminal 56 12-2 electrically couples to the first plurality of particles 21 - 2 for charge transport.
- a separator 53 is provided between the first electrode 52 - 1 and the second electrode 52 - 2 .
- An electrolyte 58 contacts the first electrode 52 - 1 and the second electrode 52 - 2 for transporting electrical charges between the first electrode 52 - 1 and the second electrode 52 - 2 using electrolyte ions.
- the electroactive electrodes 52 - 1 and 52 - 2 undergo reactions that take place in an electrolyte solution 58 , for example KOH, at the interfaces of the electroactive electrodes 52 - 1 and 52 - 2 using electrolyte ions. Electrons transfer between the electroactive electrodes 52 - 1 and 52 - 2 and the electrolyte solution 58 or dissociated species of the electrolyte, nK 1+ and nOH 1 ⁇ .
- an electrolyte solution 58 for example KOH
- the electrolyte solution 58 reacts with the material 5 - 1 and particularly the particles 21 - 1 , clusters 30 - 1 .
- the electrolyte solution 58 reacts with the nanoclusters 32 and couples directly with the composite layer 34 , the nanocluster binder 31 and the carbon nanosphere core 33 .
- the electrolyte is in one example potassium hydroxide, KOH.
- the process of electron production involves the species nOH 1 ⁇ from solution contacting a cluster such as cluster 30 - 1 .
- a cluster such as cluster 30 - 1 .
- the species nOH 1 ⁇ balances the charges imposed on the nanoclusters 32 , nanocluster binder 31 and the carbon nanosphere core 33 to form the ionic double layer.
- the reaction of the species nOH 1 ⁇ is efficient when the electrolyte solution 58 is in contact with the surface located nanoclusters clusters 32 and nanocluster binder 31 and hence where the diffusion path of the species nOH 1 ⁇ is short, typically 10 nanometers or less. Because the diffusion path of the species nOH 1 ⁇ is short, the diffusion rate is fast.
- the internal nanoclusters 32 ′, the internal nanocluster binder 31 and the carbon nanosphere core 33 are efficiently coupled for electron production by reaction with the species nOH 1 ⁇ through intercalation and close proximity of the internal nanoclusters 32 ′, the internal nanocluster binder 31 and the carbon nanosphere core 33 .
- the intercalation distance is short, typically 80 nanometers or less and hence the intercalation rate is fast.
- the process of electron recombination involves the ion nOH 1 from solution contacting a cluster such as cluster 30 - 2 .
- a cluster such as cluster 30 - 2
- the ion nOH 1 ⁇ reacts with nanoclusters 32 and with nanocluster binder 41 and with the carbon nanosphere core 33 .
- the reaction of the ion nOH 1 ⁇ is efficient when the electrolyte solution 58 is in contact with the surface located nanoclusters clusters 32 , zinc sulfide clusters and nanocluster binder 31 . Because the diffusion path of the species the ion nOH 1 ⁇ is short, typically 10 nanometers or less, the diffusion rate is fast.
- the process is the reverse of electron production.
- the recharging operation involves the species nOH 1 ⁇ from solution contacting a cluster such as cluster 30 - 2 .
- a cluster such as cluster 30 - 2 .
- the species nOH 1 ⁇ reacts with nanoclusters 32 , with nanocluster binder 31 and with the carbon nanosphere core 33 .
- the reaction of the species nOH 1 ⁇ is efficient when the electrolyte solution 58 is in contact with the surface located nanoclusters clusters 32 and nanocluster binder 31 and hence where the diffusion path of the species nOH 1 ⁇ is short, typically 10 nanometers or less. Because the diffusion path of the species nOH 1 ⁇ is short, the diffusion rate is fast.
- the internal nanoclusters 32 ′, the internal nanocluster binder 31 and the carbon nanosphere core 33 are efficiently coupled for electron production by reaction with the species nOH 1 ⁇ through intercalation and close proximity of the internal nanoclusters 32 ′, the internal nanocluster binder 31 and the carbon nanosphere core 33 .
- the intercalation distance is short, typically 80 nanometers or less and hence the intercalation rate is fast.
- the species, the species nK 1+ has interacted with ZnS.
- the process of electron recombination involves the ion nK 1+ from solution contacting a cluster such as cluster 30 - 1 .
- a cluster such as cluster 30 - 1 .
- the ion nK 1+ reacts with nanoclusters 32 , and with nanocluster binder 31 and with the carbon nanosphere core 33 .
- the reaction of the ion nK 1+ is efficient when the electrolyte solution 58 is in contact with the surface located nanoclusters clusters 32 , zinc sulfide clusters and nanocluster binder 31 . Because the diffusion path of the species the ion nK 1+ is short, typically 10 nanometers or less, the diffusion rate is fast.
- the nanomaterial 5 is formed of a plurality of nanocomponents including nanoparticles 21 , in turn formed of conductive carbon-based clusters 30 bound together by a conductive carbon-based cluster binder 22 including zinc sulfide nanoclusters 32 and nanocluster binders, all having high densities of mobile charge carriers (electrons, electronic acceptors, ionic species).
- the nanomaterial 5 plays a key role in the process of charge transport including supplying electrons (at the anode 52 - 1 and 52 - 2 ).
- the charge transport occurs by the electron travel through the highly conductive and relatively short path of the binders 22 and 31 with proximity to the nanoclusters 32 .
- the small sizes of the particles 21 provide large surface areas. In general, particle sizes of less than about 100 nanometers are preferred in order to have large surface areas which provide ready access of the electrolyte 58 to all the nanocomponents of the particles 21 .
- the combination of the high density of available electrons in all the nanocomponents of the particles 21 with the short distances among all the nanocomponents of the particles 21 and the large surface areas of the nanocomponents greatly enhances the energy and power densities achieved.
- the density of clusters producing electrons tends to be high resulting in high energy densities greater than 100 watt-hours/kilogram. Because of the short nanodistances of the particles of the present invention, the intercalation rate is fast resulting in high power densities, for example, greater than 2000 watts/kilogram.
- This efficiency of the production of electrons with the nanostructure elements of the present invention is distinguished from the inefficiency in conventional batteries where the electrodes are formed with materials having larger-sized particles and where the intercalation distance is long, typically 800 nanometers or more and the intercalation rate is slow.
- the electron transfer can occur at an electrode through the release of chemical energy to create an internal voltage or through the application of an external voltage.
- FIG. 13 depicts an electron-microscope scan of a particle 21 including composites having zinc sulfide nanoclusters.
- the particle 21 has a dimension P that is typically less than 100 nanometers, approximately 1 ⁇ 10 ⁇ 7 meters.
- the electron-microscope scan of FIG. 13 was produced with 60,000 ⁇ magnification using a Transmission Electron Microscope with a scan time of approximately one minute.
- a slide was prepared by dissolving 1 milligram of material into 20 milliliters of methanol in a scintillation vial, sonicating for 5 minutes and placing a 70 micro liter aliquot drop onto a TEM copper grid for imaging. The grid is then covered and placed in an environmental chamber to evaporate the methanol.
- the example of FIG. 13 is typical of many samples.
- a plurality of zinc-sulfide clusters 30 - 1 are shown, including among others clusters 30 - 1 1 , 30 - 1 2 , 30 - 1 3 , 30 - 1 4 , . . . , 30 - 1 12 .
- the cluster 30 - 1 1 includes a carbon nanosphere core 33 , surrounded by a composite layer 34 , having a large number of nanoclusters 32 (only two of which are labeled but includes many more as a function of the zinc sulfide packing density) held together by a nanocluster binder 31 1 .
- Each of the others clusters 30 - 1 1 , 30 - 1 2 , 30 - 1 3 , 30 - 1 4 , . . . , 30 - 1 12 has similar structures.
- the plurality of zinc-sulfide nanoclusters 30 - 1 1 , 30 - 1 2 , 30 - 1 3 , 30 - 1 4 , 30 - 1 12 are arrayed in a structure that couples the nanoclusters 30 - 1 for energy transfer (electrical, thermal, photon, mechanical and other). It is evident in FIG. 13 that nanoclusters 30 - 1 1 , 30 - 1 2 , 30 - 1 3 , 30 - 1 4 , . . . , 30 - 1 12 are linked together to form a serial chain whereby the composite layer 34 of one cluster are in close proximity to the composite layer 34 of one or more adjacent nanoclusters.
- linking of nanostructures to provide the enhanced performance that derives from efficient electrical coupling and charge transport.
- the linking is achieved by close proximity binding of the clusters with conductive composite binders.
- the linking is further enhanced by the structure of the nanoclusters based upon carbon nanocores encased in a conductive carbon-based nanocluster binder. This linking is achieved as a result of the control of char formation in tire pyrolysis.
- This linking in the present invention is superior to nanotube technology where the linking is not in-situ provided, but must be added at great expense and with high difficulty.
- FIG. 13 is a planar view of a thin plane of nanomaterial representing a monolayer of material, but it should be noted that the close proximity of the composite layers 34 occurs in three dimensions of a volume of material.
- the close proximity of composite layers 34 and the resultant high energy transfer characteristics of the nanomaterials are determined as a function of the processing times, temperatures and pressures during pyrolysis of tires.
- FIG. 14 depicts an enlarged view of a portion of the electron-microscope scan of the cluster 30 - 1 9 adjacent to and in close proximity to the cluster 30 - 1 8 of FIG. 13 .
- the composite layers 34 8 and 34 9 of clusters 30 - 1 8 and 30 - 1 9 are in close proximity.
- the cluster 30 - 1 9 includes, by way of example, nanoclusters 32 9-1 , 32 9-2 and 32 9-3 .
- the nanoclusters 32 9-1 , 32 9-2 and 32 9-3 are bound together in the composite layer 34 9 by the nanocluster binder 31 9 .
- the zinc sulfide properties of the nanoclusters 32 9-1 , 32 9-2 and 32 9-3 are identified by in-situ x-ray backscattering images observed during the scan.
- the other materials present include many of the materials of TABLE 2 in varying concentrations that are generally less than the concentration of zinc sulfide.
- the concentration of pyrolitic carbon is typically greater than the concentration of zinc sulfide.
- the pyrolitic carbon in the composite 34 facilitates the ion formation and charge transport.
- the other materials of TABLE 2 may also play a contributing role to the operation.
- FIG. 15 depicts an electron-microscope scan showing further details of the nanocluster of FIG. 14 .
- FIG. 16 depicts an electron-microscope scan showing even further details of the nanocluster of FIG. 15 .
- the nanocluster 32 9-3 is much larger than the nanocluster 32 9-4 and demonstrates that the zinc sulfide nanocluster have widely varying size distributions.
- the manufacturing process for forming electrochemical capacitors from tire char is as follows.
- the carbon char from pyrolyzed tires is ground or otherwise formed into a fine powder with a particle size distribution that includes a substantial number of small particles, that is, particles measuring less than 100 nanometers.
- the resultant fine powder is mixed with an electrolyte solution consisting of approximately 38% NaOH in distilled water at a ratio of 4 g fine powder (carbon) to 3.5 g of electrolyte.
- This carbon/electrolyte mixture is then ground (if done by hand using a mortar and pestle) for approximately 10 minutes or until the electrode material has a smooth consistency.
- the ground electrode material can be stored for weeks or more in a sealed container.
- Capacitors are assembled by rolling out the electrode material in a thin layer onto a current collector which, for example, is 316 stainless steel foil supported by a rigid member such as plate glass.
- a separator is placed atop the thin layer of electrode material.
- the separator consists of an ion permeable, electrically insulating membrane (Pall Rai membrane) which is pre-saturated with electrolyte solution by soaking in the electrolyte solution for longer than 30 minutes.
- Another layer of electrode material is placed atop the insulating membrane to form a symmetrical electrode, followed by a collector plate.
- the capacitor layers are then compressed, for example using clips, sealed with epoxy and allowed to cure at 50° C. for an hour. After the epoxy has cured, the binder clips are removed. The resulting electrochemical capacitors are tested.
- the capacitors are tested by first charging to 0.75V until the current required to maintain this charge level falls below 1 milliamp. The capacitors are then cycled through charge/discharge cycles whereby the charging current is reversed until the potential at the collector reaches 0V. Then the current is switched to charge the capacitors back to their previous potential. The time required to discharge and recharge the cell is recorded as is the current used and the total voltage change. These values along with the carbon mass in each electrode are used to calculate the energy stored in the cell.
Abstract
Description
- The present invention relates to electrodes and electrochemical devices having electrodes that undergo electrochemical reactions and particularly to nanomaterial electrodes and devices.
- Nanomaterials are materials that include components with nanometer dimensions, for example, where at least one dimension is less than 100 nanometers. Examples of such materials are allotropes of carbon such as nanotubes or other carbon fullerenes and components of carbon char. Carbon black was an early use of nanomaterials in tire manufacturing. Other nanomaterials include inorganic materials such as metal sulfides, metal oxides and organic materials. Because of the small dimensions, nanomaterials often exhibit unique electrical and electrochemical properties and unique energy transport properties. These properties are most pronounced when high surface areas are present and when charge transport mechanisms exist in the nanomaterials.
- Some nanomaterials are manufactured using rigorous processing steps that are expensive and commercially unattractive. Some nanomaterials occur naturally or incidentally in commercial processing steps. Naturally or incidentally occurring nanomaterials tend to be highly irregular in size and composition because the environment in which they are produced is not adequately controlled for the production of nanomaterials. Processing methods that produce nanomaterials include among others, liquid-phase steps, gas-phase steps, grinding steps, size-reduction steps and pyrolysis steps.
- Pyrolysis is the heating of materials in the absence of oxygen to break down complex matter into simpler molecules and components. When carbon based materials are pyrolyzed, the process of carbonization can occur leading to an ordered state of semi-graphitic material. When carbon based materials are pyrolyzed in uncontrolled conditions, a large amount of randomly ordered carbon material results. When both carbon and inorganic materials are present, pyrolysis under controlled conditions can lead to highly useful and unique results. An example of a use of pyrolysis is for the break down of used tires (typically from automobiles, trucks and other vehicles). The pyrolysis of tires results in, among other things, a carbon/inorganic residue called char.
- The composition of char from tire pyrolysis is determined by the materials that are used to manufacture tires. The principal materials used to manufacture tires include rubber (natural and synthetic), carbon black (to give strength and abrasion resistance), sulfur (to cross-link the rubber molecules in a heating process known as vulcanization), accelerator metal oxides (to speed up vulcanization), activation inorganic oxides (principally zinc oxide, to assist the vulcanization), antioxidant oxides (to prevent sidewall cracking), a textile fabric (to reinforce the carcass of the tire) and steel belts for strength. The carbon black has a number of carbon structures including graphitic spheroids with nanometer dimensions, semi graphitic particles and other forms of ordered carbon structures.
- In summary, the manufacture of tires initially mixes the materials to form a “green” tire where the carbons and oxides form a homogenous mixture. The “green” tire is transformed into a finished tire by the curing process (vulcanization) where heat and pressure are applied to the “green” tire for a prescribed “cure” time. The carbon materials used in “green” tires are typically as indicated in TABLE 1:
-
TABLE 1 DESIGNATION SIZE (nm) N110 20-25 N220 24-33 N330 28-36 N300 30-35 N550 39-55 N683 49-73 - When tires are discarded, they are collected for pyrolysis processing to reclaim useful components of the tires. In general, tire pyrolysis involves the thermal degradation of the tires in the absence of oxygen. Tire pyrolysis has been used to convert tires into value-added products such as pyrolytic gas (pyro-gas), oils, char and steel. Pyrolysis is performed with low emissions and other steps that do not have an adverse impact on the environment. The basic pyrolysis process involves the heating of tires in the absence of oxygen. To enhance value, the oils and char typically under go additional processes to provide improved products.
- In electrochemical capacitors, electrical charge is stored on the surface of an electrically conductive electrode material. The capacitance arises by separation of electrons at the electrode surface and ionic charges in the electrolyte solution. Because the charge separation arises over only a distance of 0.1 to 10 nanometers, large specific capacitances can be achieved on the order of 10-20 microfarads per square centimeter of electrode material. The larger the surface area of the electrode material, the greater the charge that can be stored. Since the capacitance, or the amount of charge that an electrochemical capacitor can hold, is directly related to the surface area of the electrodes, electrodes made from conductive materials with high surface areas are preferred. Devices incorporating such electrodes are referred to as double layer capacitors or supercapacitors.
- Electrochemical capacitors are charge-storage devices that are capable of delivering high power densities and that are capable of being cycled (charged and discharged) millions of times, hence demonstrating a significant advantage over conventional batteries. Electrochemical capacitors have energy and power capabilities that lie between the capabilities of a battery and of a conventional capacitor (electrolytic, thin film and others).
- There is substantial demand for a rechargeable energy source that can provide high power and energy densities, can be charged quickly, has a high cycle life is environmentally benign and cost effective. Double layer capacitors, especially when used in conjunction with batteries, are rechargeable charge storage devices that fulfill this need.
- In prior art capacitors, the production of activated carbon is an energy intensive process that first includes heating of a precursor material (natural or synthetic) to form a carbon powder or carbon fiber, in many cases requiring temperatures up to 3000° C. Next, to form activated carbon, the material is heated to about 800° C. in an atmosphere of steam or carbon dioxide, or electrochemical reaction in a strongly oxidizing solutions (such as Hummers reagent) to produce a carbon with high surface area to provide high energy density and high power density. Overall, the yield for activated carbons is generally not better than 25% based on weight of the precursor material.
- A single cell double-layer capacitor consists of two electrodes which store electrical charge (called the active materials), separated by an ion permeable but electrically insulating membrane. Each electrode is also in contact with a current collector which provides for electrical contact outside of the cell. The electrodes and membrane are infused with an electrolyte and enclosed in an inert housing which provides a sealed environment and also enough compression to reduce contact resistance between the different layers. Multiple cells may be used in series to increase the allowable potential (voltage), and also in parallel to increase the capacitance.
- Applying an electrical potential across the electrodes causes charge to build up in the electrochemical double layer that exists at the electrode/electrolyte interface for each electrode. This process continues until a state of equilibrium is reached, so that the potential of the electrodes is at the charging potential and the current is reduced to that required to maintain the charge.
- Because carbon is relatively chemically inert, has a high electrical conductivity, is environmentally benign, and is relatively inexpensive, some forms of carbon are excellent materials for fabricating electrodes. However, many forms of carbon are not suitable for electrodes. The desired properties of the electrochemical capacitor electrodes include the following high surface area, electrically conductive, low cost, readily available source of material and long-term stability under operating conditions.
- Advances are being made in electrochemical capacitor technology research using nanomaterials. While capacitors of many types are known, there is a need for improved electrodes based on nanomaterials and for new electrochemical capacitors using the new nanomaterials.
- The present invention is an electroactive material for charge storage and transport in an electrochemical capacitor. The material is formed of a plurality of nanocomponents including nanoparticles, in turn formed of conductive carbon-based clusters bound together by a conductive carbon-based cluster binder including zinc sulfide nanoclusters and nanocluster binders, all having high densities of mobile charge carriers (electrons, electronic acceptors, ionic species). A terminal is electrically coupled to the nanoparticles for charge transport.
- The material and each of the nanocomponents play key roles in the process of charge transport including supplying electrons and electron acceptor sites. The charge transport occurs by the electron travel through the highly conductive and relatively short path of the binders with proximity to the nanoclusters. The small sizes of the particles provide large surface areas. In general, particle sizes of less than about 100 nanometers are preferred in order to have large surface areas which provide ready access of the electrolyte to the nanocomponents of the particles. The combination of the high density of available electrons in all the nanocomponents of the particles with the short distances among all the nanocomponents of the particles and the large surface areas of the nanocomponents greatly enhances the energy and power densities achieved.
- Because of the short nanodistances of the particles, the density of clusters producing electrons tends to be high resulting in high energy densities. Because of the short nanodistances of the particles, the intercalation rate is fast resulting in high power densities, for example, greater than 1000 watts/kilogram. In a further embodiment, a second electroactive material is provided for charge transport. The second material is formed of a second plurality of nanocomponents including second nanoparticles, in turn formed of conductive carbon-based clusters bound together by a conductive carbon-based cluster binder including nanoclusters and nanocluster binders, all having high densities of mobile charge carriers (electrons, electronic acceptors, ionic species). A second terminal is electrically coupled to the nanoparticles for charge transport.
- In a further embodiment, the second plurality of particles are substantially the same as the first plurality of particles including zinc sulfide nanoclusters.
- In a further embodiment, the second plurality of particles are substantially different from the first plurality of particles including zinc sulfide nanoclusters.
- In a further embodiment, the zinc sulfide nanoclusters are charge receptors and wherein charge transport uses electrolyte ions.
- In a further embodiment, the second plurality of particles are separated from the first plurality of particles by an ion permeable membrane.
- In a further embodiment, the carbon nanosphere cores have diameters of less than approximately 100 nanometers.
- The electroactive material of
claim 2 wherein the composite layer has a wall thickness of less than approximately 1200 nanometers. - In a further embodiment, a substantial number of the clusters have diameters of less than approximately 1200 nanometers.
- The foregoing and other objects, features and advantages of the invention will be apparent from the following detailed description in conjunction with the drawings.
-
FIG. 1 is a schematic representation of material formed of particles including composites having nanoclusters. -
FIG. 2 depicts a schematic representation of a typical particle of theFIG. 1 material including composites having nanoclusters. -
FIG. 3 depicts a schematic representation of a typical composite having zinc sulfide nanoclusters. -
FIG. 4 depicts a schematic representation of a typical composite having zinc nanoclusters. -
FIG. 5 depicts an electroactive material having nanoparticles and having a terminal electrically coupled to the particles for charge transport. -
FIG. 6 depicts a device including first and second electroactive materials of theFIG. 5 type, each having nanoparticles and having a terminal electrically coupled to the particles for charge transport. -
FIG. 7 depicts a device including a first electroactive material including a second electroactive material, different from the first electroactive material, having nanoparticles and having a terminal electrically coupled to the particles for charge transport. -
FIG. 8 depicts a device including first and second electroactive materials and including a third electroactive material, like the first electroactive material and having nanoparticles and having a terminal electrically coupled to the particles for charge transport. -
FIG. 9 depicts a schematic expanded representation of an electrochemical capacitor having one electrode formed of particles including composites having zinc sulfide nanoclusters (anode) and another electrode formed of particles including composites having zinc sulfide nanoclusters (cathode). -
FIG. 10 depicts a schematic expanded representation of a electrochemical capacitor of theFIG. 9 type having added spacers -
FIG. 11 depicts a schematic collapsed representation of the electrochemical capacitor of theFIG. 10 . -
FIG. 12 depicts a representation of an anode and cathode formed of electroactive materials. -
FIG. 13 depicts an electron-microscope scan of a particle including composites having zinc sulfide nanoclusters. -
FIG. 14 depicts an electron-microscope scan of one of the nanoclusters ofFIG. 13 . -
FIG. 15 depicts an electron-microscope scan showing further details of the nanocluster ofFIG. 14 . -
FIG. 16 depicts an electron-microscope scan showing even further details of the nanocluster ofFIG. 15 . - The electrode materials used in electrochemical capacitors serve multiple concurrent functions by acting both as a battery and an electrochemical capacitor with tunable power and energy capabilities. The cost of the carbon-based electrode materials is substantially reduced through use of materials derived from tire pyrolysis. These nanosized carbon-based materials are preferred materials for the electrodes in electrochemical capacitors due to their large surface areas and high charge densities. The large surface areas and high charge densities are accessible to the charge carrying electrolyte ions. Highly accessible surface areas and high charge densities are important for high energy density and high power density.
- The char obtained from the pyrolysis of tires is an inexpensive source of nanomaterials that, with further control and added processing, are potentially useful in many fields including Photo Catalysts, Contact Catalysts, Capacitors, Batteries, Sorbents (Adsorbents and Absorbents) and Photo Voltaic Materials. The ability to use nanomaterials derived from char in useful applications is dependent on controlling the parameters of the tire pyrolysis process and the processing of char for particular applications.
- One particular application of processed char is for electrodes that are used in batteries, electrochemical capacitors and other devices. In general, electrodes undergo reactions that take place in a solution at the interface of an electron conductor (electrode) and an ionic conductor (electrolyte). Electrons transfer between the electrode and the electrolyte or species in solution. Typical electrolytes include aqueous, organic, inorganic and polymeric.
- The electron transfer can occur at an electrode through the release of chemical energy to create an internal voltage or through the application of an external voltage. Electrochemical reactions transfer electrons between atoms or molecules. These reactions can be separated in space and time and devices with such reactions are often connected to external electric circuits. The creation of internal voltages at electrodes is useful in electrochemical capacitors.
- One example of batch pyrolysis uses a furnace/retort, a three stage condensing system, a water scrubber, and a flare. An oil tank collects the condensed oil at the end of each test. The furnace uses two burners. The operating temperature of the furnace is set at 1,750° F. with a control range of plus/minus 30 to 40° F. When the control temperature is reached, one burner is shut off continuing with a small upward drift in temperature. When the temperature drifts down, the burner restarts automatically. Both burners are on for the first 90 minutes. Burner cycle time after the start of the run is a few seconds; near the end of the run, one burner is off for period as long as three minutes with a like interval of being on. Exhaust gas temperature remains relatively stable between 1,250 and 1380° F. Pyro gas generation starts after 105 minutes of operation at a temperature of 650° F., reached a high of 700° F., and dropped to 375° F. at the end of the thermal cycle.
- The control of the temperatures and the control of the heating and cooling rates during pyrolysis are critical for producing the nanocomponents having the nano structures of the present invention.
- The thermal operation is monitored using the back pressure in the retort, the cooling water temperature, and visually watching the flare. A run lasts approximately 16 hours. At the end of the run, the furnace back pressure is almost atmospheric, the cooling water delta temperature is almost zero, and the flare is out. During this operational period, the ambient air temperature ranged from about 20 to 45° F. The retort is opened approximately 8 hours after the thermal cycle is shut down. The estimated temperature of the char is less than 350° F. Prior to opening the retort, the retort is purged with nitrogen for a brief period of time. After the lid is opened, a very small quantity of vapor comes from the remaining char and tire wire. Cooling water flow (rate and temperature) is monitored as a check of the process gas generation rate and the condensing duty for both the condensable and non-condensable fraction of the process gas produced. When the inlet and outlet temperatures of the cooling water measures about the same, the operation is complete. The operating pressure of the retort ranges from two to eight millibars above atmospheric, which is sufficient to transport the gas through the condensing system to the flare. For the example described, the tire charge was 3,400 pounds in eight bales. The eight bales averaged 15 tires, with an average weight of 28 pounds per tire. The output yield of char was approximately 25% or more of the tire input.
- After pyrolysis of tires, the composition of char, for one typical example, includes carbon as previously indicated in TABLE 1 and includes inorganic materials, such as metal sulfides and metal oxides, as indicated in the following TABLE 2:
-
TABLE 2 MATERIAL FORMULA x RANGE Aluminum oxide (Al) Al2O(3−x)Sx 0 to 3 Barium oxide (Ba) BaO(1−x)Sx 0 to 3 Bismuth oxide (Bi) Bi2O(3−x)Sx 0 to 3 Calcium oxide (Ca) CaO(1−x)Sx 0 to 1 Chromium oxide (Cr) Cr2O(3−x)Sx 0 to 3 Iron oxide (Fe) Fe2O(3−x)Sx 0 to 3 Iron oxide (Fe) FeO(2−x)Sx 0 to 2 Lead oxide (Pb) FeO(1−x)Sx 0 to 1 Magnesium oxide (Mg) MgO(1−x)Sx 0 to 2 Manganese oxide (Mn) Mn2O(3−x)Sx 0 to 3 Molybdenum oxide (Mo) Mo2O(3−x)Sx 0 to 3 Molybdenum oxide (Mo) MoO(2−x)Sx 0 to 2 Phosphorous oxide (P) P2O(5−x)Sx 0 to 5 Potassium oxide (K) K2O(1−x)Sx 0 to 1 Silicon oxide (Si) SiO(2−x)Sx 0 to 2 Sodium oxide (Na) Na2O(1−x)Sx 0 to 2 Stronium oxide (Sr) SrO(1−x)Sx 0 to 1 Titanium oxide (Ti) Ti2O(3−x)Sx 0 to 3 Titanium oxide (Ti) TiO(2−x)Sx 0 to 2 Zinc oxide (Zn) ZnO(1−x)Sx 0 to 1 Other Metal oxides (trace) Pyrolitic Carbon C6mCn m > n (aromatic) - The combination of TABLE 1 materials and TABLE 2 materials as produced by the pyrolysis process form nanomaterial composites useful in many fields including Photo Catalysts, Contact Catalysts, Capacitors, Batteries, Sorbents (Adsorbents and Absorbents) and Photo Voltaic Materials.
- The TABLE 2 materials are “heavy metal free” in that even if trace amounts of heavy metals were produced as a result of tire pyrolysis, the trace amounts are so small that no environmental hazard is presented.
- In
FIG. 1 , thematerial 5 includes nanomaterial in the form ofparticles 21 derived from char in the manner previously described. Typically, the char is processed for size reduction, sorting, classification and other attributes to form thechar particles 21. - In
FIG. 2 , a schematic representation of aparticle 21 is shown that is typical of theparticles 21 in thematerial 5 ofFIG. 1 . In embodiments where thematerial 5 is used in an electrode, theparticles 21 ofFIG. 1 typically have at least one dimension, P, in a range from approximately 10 nm to approximately 10,000 nm. InFIG. 2 , theparticle 21 includes a plurality ofclusters 30 that are held together by acluster binder 22. The material of thecluster binder 22 primarily contains components of TABLE 1 and TABLE 2. - In the
particle 21, a number of theclusters 30 are externally located around the periphery of theparticle 21 and a number of theclusters 30, designated asclusters 30′, are located internally away from the periphery ofparticle 21. The internally locatedclusters 30′ are loosely encased by thecluster binder material 22. The selection of particle sizes in a range from approximately 50 nm to approximately 1000 nm tends to optimize the number of active and externally locatedclusters 30 and thereby enhances the electrochemical operations of the electrodes. The internally locatedclusters 30′ are efficiently coupled electrically and through intercalation. - In
FIG. 3 , a schematic representation is shown of a cluster 30-1 that is typical of one embodiment ofclusters 30 ofFIG. 2 . The cluster 30-1 has a graphiticcarbon nanosphere cores 33 encased by acomposite layer 34. Thecarbon nanosphere core 33 is generally spherical in shape (a nanosphere) and has a core diameter, DC1, in a range from approximately 10 nanometers to approximately 1000 nanometers. Thecomposite layer 34 has a wall thickness, WT1, in a range from approximately 0.2 nanometers to approximately 300 nanometers. The overall diameter of the cluster 30-1 (DC1+WT1) in a range from approximately 10 nanometers to approximately 1300 nanometers. - In
FIG. 3 , the size and shape of thecarbon nanosphere cores 33 are limited primarily by the size and the shape of the cores used in the mixture forming the “green” tires as indicated in TABLE 1. The melting point of graphite is approximately in the range from 1900° C. to 2800° C. Since both the vulcanization and the pyrolysis processes operate at much lower temperatures, thecarbon nanosphere cores 33 in finished tires and in tire char remain essentially undisturbed from their original size and shape. - In
FIG. 3 , thecomposite layers 34 surrounds and incases thecarbon nanosphere cores 33. The sizes and the shapes of thecomposite layers 34 are determined in part by the sizes and the shapes of thecarbon nanosphere cores 33 and additionally by the processing of the tire char. The processing of the char is done so as to achieve the 0.2 nanometers to approximately 300 nanometers for the wall thickness, WT1, and so as to achieve the overall diameter, (DC1+WT1), of the clusters 30-1 in a range from approximately 10 nanometers to approximately 1300 nanometers. - In
FIG. 3 , thecomposite layer 34 is carbon and contains a mixture of metal oxides and metal sulfides of TABLE 2 and other materials as described in TABLE 1, surrounding and bound to thecarbon nanosphere core 33. Specifically, thecomposite layer 34 includeszinc sulfide nanoclusters 32 embedded in and forming part of thecomposite layer 34. A number of thenanoclusters 32 are externally located, that is, located around the periphery of the cluster 30-1 and a number of thenanoclusters 32, designated asnanoclusters 32′, are located internally away from the periphery of thecomposite layer 34. The composition of thecomposite layer 34 typically has zinc sulfide (ZnS) in a range, for example, of 2% to 20% by weight, and carbon and other components of TABLE 2. - In
FIG. 4 , a schematic representation is shown of a cluster 30-2 that is typical of one embodiment ofclusters 30 ofFIG. 2 . The cluster 30-2 has acarbon nanosphere core 43 encased by acomposite layer 34. Thecarbon nanosphere core 43 is generally spherical in shape (a nanosphere) and has a core diameter, DC2, in a range from approximately 10 nanometers to approximately 1000 nanometers. Thecomposite layer 34 has a wall thickness, WT2, in a range from approximately 0.2 nanometers to approximately 300 nanometers. The overall diameter of the cluster 30-2 (DC2+WT2) in a range from approximately 10 nanometers to approximately 1300 nanometers. - In
FIG. 4 , the size and shape of thecarbon nanosphere cores 43 are limited primarily by the size and the shape of the cores used in the mixture forming the “green” tires as indicated in TABLE 1. The melting point of graphite is approximately in the range from 1900° C. to 2800° C. Since both the vulcanization and the pyrolysis processes operate at much lower temperatures, thecarbon nanosphere cores 43 in finished tires and in tire char remain essentially undisturbed from their original size and shape. - In
FIG. 4 , thecomposite layers 34 surrounds and incases thecarbon nanosphere cores 43. The sizes and the shapes of thecomposite layers 34 are determined in part by the sizes and the shapes of thecarbon nanosphere cores 43 and additionally by the processing of the tire char. The processing of the char is done so as to achieve the 0.25 nanometers to approximately 80 nanometers for the wall thickness, WT2, and so as to achieve the overall diameter, (DC2+WT2), of the clusters 30-2 in a range from approximately 5 nanometers to approximately 100 nanometers. - In
FIG. 4 , thecomposite layer 34 is a mixture of metal oxides and metal sulfides of TABLE 2 and other materials as described in TABLE 1, surrounding and bound to thecarbon nanosphere core 43. Specifically, thecomposite layer 34 includeszinc sulfide nanoclusters 32 embedded in and forming part of thecomposite layer 34. A number of thenanoclusters 32 are externally located, that is, located around the periphery of the cluster 30-2 and a number of thenanoclusters 32, designated asnanoclusters 32′, are located internally away from the periphery of thecomposite layer 34. The composition of thecomposite layer 34 typically has zinc sulfide (ZnS) in a range from approximately 2% to approximately 20% by weight, carbon in a range from approximately 60% to approximately 70% by weight, with the balance of thecomposite layer 34 principally being a mixture of metal oxides and metal sulfides of TABLE 2 and other materials as described in TABLE 1. -
FIG. 5 depicts anelectroactive material 21 5 having nanoparticles and having a terminal 565 electrically coupled to the particles for charge transport. The terminal 565 functions as an electrode for allowing charge transport to and from the particles forming thenanomaterial 21 5. -
FIG. 6 depicts a device including first and second electroactive materials 21-1 6 and 21-2 6 of theFIG. 5 type, each having nanoparticles and having terminals 56-1 6 and 56-2 6 electrically coupled to the particles of the first and second electroactive materials 21-1 6 and 21-2 6, respectively, for charge transport. -
FIG. 7 depicts a device including a first electroactive material electroactive material 21-1 7 of theFIG. 5 type and having terminals 56-1 7 and including a second electroactive material 21-2 7, different from the first electroactive material, having nanoparticles and having a terminal 56-2 7 electrically coupled to the particles for charge transport. -
FIG. 8 depicts a device a device including first and second electroactive materials 21-1 8 and 21-2 8 of theFIG. 5 type, each having nanoparticles and having terminals 56-1 8 and 56-2 8 electrically coupled to the particles of the first and second electroactive materials 21-1 8 and 21-2 8, respectively, for charge transport and including a third electroactive material 21-3 8, like the first electroactive material and having nanoparticles and having a terminal 56-3 8 electrically coupled to the particles for charge transport. - In
FIG. 9 , a schematic representation of anelectrochemical capacitor 50 is shown having one electrode (anode) 52 and another electrode (cathode) 54. Theanode 52 is formed ofparticles 21 as described in connection withFIG. 1 ,FIG. 2 andFIG. 3 and includescluster 30 and specifically cluster 30-1 havingzinc sulfide nanoclusters 32. Thecathode 54 is formed ofparticles 21 as described in connection withFIG. 1 ,FIG. 2 andFIG. 3 and includescluster 30 and specifically cluster 30-2 havingzinc sulfide nanoclusters 32. - In
FIG. 9 , the electrode (anode) 52 and electrode (cathode) 54 are immersed in asolution 58 which in one example is 38% potassium hydroxide, KOH, in water. Aseparator 53 is provided between theanode 52 and thecathode 54. Theseparator 53 is a membrane which pre-vents any carbon transfer or contact between theanode 52 and thecathode 54 while permitting the transport of electrolyte ions. Theanode 52 contacts a metal or other good-conductingmaterial 51 to enable electron flow atterminal 56. Thecathode 54 contacts a metal or other good-conductingterminal connector 55 to enable electron flow atcontact 57. Thecapacitor elements - In
FIG. 10 , a schematic representation ofcapacitor 50 ofFIG. 9 is shown having the addition ofspacers spacer 560 is between theanode 52 and themembrane separator 53. Thespacer 570 is between thecathode 54 and themembrane separator 53. Thespacers capacitor 50 and also provide hermetic seals that constrain theelectrolyte 58. Thecapacitor elements - In
FIG. 11 , a schematic representation ofcapacitor 50 ofFIG. 6 is shown without expanded spacing. - In
FIG. 12 , thecapacitor 50 shown inFIG. 9 ,FIG. 10 andFIG. 11 is shown with greater details of the nanoscale structure of the materials and of the charge transport. - In
FIG. 12 , thecapacitor 50 includes a first electroactive electrode 52-1 including a material 5-1 formed of plurality of particles 21-1. Each includes a plurality of clusters, of which cluster 30-1 is typical. Each cluster includes acarbon nanosphere core 33, acomposite layer 34 surrounding and bound to thecarbon nanosphere core 33. Thecomposite layer 34 includeszinc sulfide nanoclusters 32 embedded in thecomposite layer 34, and a bindingcomposite 31 binding the plurality ofnanoclusters 32. Afirst terminal 56 12-1 electrically couples to the first plurality of particles 21-1 for charge transport. - A second electroactive electrode electroactive electrode 52-2 including a material 5-2 formed of plurality of particles 21-2. Each includes a plurality of clusters, of which cluster 30-2 is typical. Each cluster includes a
carbon nanosphere core 33, acomposite layer 34 surrounding and bound to thecarbon nanosphere core 33. Thecomposite layer 34 includeszinc sulfide nanoclusters 32 embedded in thecomposite layer 34, and a bindingcomposite 41 binding the plurality ofnanoclusters 32. Asecond terminal 56 12-2 electrically couples to the first plurality of particles 21-2 for charge transport. - A
separator 53 is provided between the first electrode 52-1 and the second electrode 52-2. Anelectrolyte 58 contacts the first electrode 52-1 and the second electrode 52-2 for transporting electrical charges between the first electrode 52-1 and the second electrode 52-2 using electrolyte ions. - In general in
FIG. 12 , the electroactive electrodes 52-1 and 52-2 undergo reactions that take place in anelectrolyte solution 58, for example KOH, at the interfaces of the electroactive electrodes 52-1 and 52-2 using electrolyte ions. Electrons transfer between the electroactive electrodes 52-1 and 52-2 and theelectrolyte solution 58 or dissociated species of the electrolyte, nK1+ and nOH1−. - When
terminals electrolyte solution 58 reacts with the material 5-1 and particularly the particles 21-1, clusters 30-1. For each cluster 30-1, theelectrolyte solution 58 reacts with thenanoclusters 32 and couples directly with thecomposite layer 34, thenanocluster binder 31 and thecarbon nanosphere core 33. The electrolyte is in one example potassium hydroxide, KOH. - The process of electron production involves the species nOH1− from solution contacting a cluster such as cluster 30-1. For each cluster the species nOH1− balances the charges imposed on the
nanoclusters 32,nanocluster binder 31 and thecarbon nanosphere core 33 to form the ionic double layer. The reaction of the species nOH1− is efficient when theelectrolyte solution 58 is in contact with the surface locatednanoclusters clusters 32 andnanocluster binder 31 and hence where the diffusion path of the species nOH1− is short, typically 10 nanometers or less. Because the diffusion path of the species nOH1− is short, the diffusion rate is fast. - Additionally, the
internal nanoclusters 32′, theinternal nanocluster binder 31 and thecarbon nanosphere core 33 are efficiently coupled for electron production by reaction with the species nOH1− through intercalation and close proximity of theinternal nanoclusters 32′, theinternal nanocluster binder 31 and thecarbon nanosphere core 33. Again, the intercalation distance is short, typically 80 nanometers or less and hence the intercalation rate is fast. - The process of electron recombination involves the ion nOH1 from solution contacting a cluster such as cluster 30-2. For each cluster 30-2, the ion nOH1− reacts with
nanoclusters 32 and withnanocluster binder 41 and with thecarbon nanosphere core 33. The reaction of the ion nOH1− is efficient when theelectrolyte solution 58 is in contact with the surface locatednanoclusters clusters 32, zinc sulfide clusters andnanocluster binder 31. Because the diffusion path of the species the ion nOH1− is short, typically 10 nanometers or less, the diffusion rate is fast. - For recharging operation, the process is the reverse of electron production. The recharging operation involves the species nOH1− from solution contacting a cluster such as cluster 30-2. For each cluster the species nOH1− reacts with
nanoclusters 32, withnanocluster binder 31 and with thecarbon nanosphere core 33. The reaction of the species nOH1− is efficient when theelectrolyte solution 58 is in contact with the surface locatednanoclusters clusters 32 andnanocluster binder 31 and hence where the diffusion path of the species nOH1− is short, typically 10 nanometers or less. Because the diffusion path of the species nOH1− is short, the diffusion rate is fast. - Additionally, the
internal nanoclusters 32′, theinternal nanocluster binder 31 and thecarbon nanosphere core 33 are efficiently coupled for electron production by reaction with the species nOH1− through intercalation and close proximity of theinternal nanoclusters 32′, theinternal nanocluster binder 31 and thecarbon nanosphere core 33. Again, the intercalation distance is short, typically 80 nanometers or less and hence the intercalation rate is fast. - At the cathode, the species, the species nK1+ has interacted with ZnS.
- The process of electron recombination involves the ion nK1+ from solution contacting a cluster such as cluster 30-1. For each cluster 30-1, the ion nK1+ reacts with
nanoclusters 32, and withnanocluster binder 31 and with thecarbon nanosphere core 33. The reaction of the ion nK1+ is efficient when theelectrolyte solution 58 is in contact with the surface locatednanoclusters clusters 32, zinc sulfide clusters andnanocluster binder 31. Because the diffusion path of the species the ion nK1+ is short, typically 10 nanometers or less, the diffusion rate is fast. - The
nanomaterial 5 is formed of a plurality ofnanocomponents including nanoparticles 21, in turn formed of conductive carbon-basedclusters 30 bound together by a conductive carbon-basedcluster binder 22 includingzinc sulfide nanoclusters 32 and nanocluster binders, all having high densities of mobile charge carriers (electrons, electronic acceptors, ionic species). - The
nanomaterial 5, and each of the nanocomponents, plays a key role in the process of charge transport including supplying electrons (at the anode 52-1 and 52-2). The charge transport occurs by the electron travel through the highly conductive and relatively short path of thebinders nanoclusters 32. The small sizes of theparticles 21 provide large surface areas. In general, particle sizes of less than about 100 nanometers are preferred in order to have large surface areas which provide ready access of theelectrolyte 58 to all the nanocomponents of theparticles 21. The combination of the high density of available electrons in all the nanocomponents of theparticles 21 with the short distances among all the nanocomponents of theparticles 21 and the large surface areas of the nanocomponents greatly enhances the energy and power densities achieved. - Because of the short nanodistances of the particles of the present invention, the density of clusters producing electrons tends to be high resulting in high energy densities greater than 100 watt-hours/kilogram. Because of the short nanodistances of the particles of the present invention, the intercalation rate is fast resulting in high power densities, for example, greater than 2000 watts/kilogram.
- This efficiency of the production of electrons with the nanostructure elements of the present invention is distinguished from the inefficiency in conventional batteries where the electrodes are formed with materials having larger-sized particles and where the intercalation distance is long, typically 800 nanometers or more and the intercalation rate is slow.
- The electron transfer can occur at an electrode through the release of chemical energy to create an internal voltage or through the application of an external voltage.
-
FIG. 13 depicts an electron-microscope scan of aparticle 21 including composites having zinc sulfide nanoclusters. Theparticle 21 has a dimension P that is typically less than 100 nanometers, approximately 1×10−7 meters. The electron-microscope scan ofFIG. 13 was produced with 60,000× magnification using a Transmission Electron Microscope with a scan time of approximately one minute. A slide was prepared by dissolving 1 milligram of material into 20 milliliters of methanol in a scintillation vial, sonicating for 5 minutes and placing a 70 micro liter aliquot drop onto a TEM copper grid for imaging. The grid is then covered and placed in an environmental chamber to evaporate the methanol. The example ofFIG. 13 is typical of many samples. - In
FIG. 13 , a plurality of zinc-sulfide clusters 30-1 are shown, including among others clusters 30-1 1, 30-1 2, 30-1 3, 30-1 4, . . . , 30-1 12. By way of example, the cluster 30-1 1 includes acarbon nanosphere core 33, surrounded by acomposite layer 34, having a large number of nanoclusters 32 (only two of which are labeled but includes many more as a function of the zinc sulfide packing density) held together by ananocluster binder 31 1. Each of the others clusters 30-1 1, 30-1 2, 30-1 3, 30-1 4, . . . , 30-1 12 has similar structures. - In
FIG. 13 , the plurality of zinc-sulfide nanoclusters 30-1 1, 30-1 2, 30-1 3, 30-1 4, 30-1 12 are arrayed in a structure that couples the nanoclusters 30-1 for energy transfer (electrical, thermal, photon, mechanical and other). It is evident inFIG. 13 that nanoclusters 30-1 1, 30-1 2, 30-1 3, 30-1 4, . . . , 30-1 12 are linked together to form a serial chain whereby thecomposite layer 34 of one cluster are in close proximity to thecomposite layer 34 of one or more adjacent nanoclusters. With such close proximity ofcomposite layers 34, energy transfer is readily facilitated from adjacent to adjacent nanoclusters. It is highly desirable to have linking of nanostructures to provide the enhanced performance that derives from efficient electrical coupling and charge transport. The linking is achieved by close proximity binding of the clusters with conductive composite binders. The linking is further enhanced by the structure of the nanoclusters based upon carbon nanocores encased in a conductive carbon-based nanocluster binder. This linking is achieved as a result of the control of char formation in tire pyrolysis. This linking in the present invention is superior to nanotube technology where the linking is not in-situ provided, but must be added at great expense and with high difficulty. -
FIG. 13 is a planar view of a thin plane of nanomaterial representing a monolayer of material, but it should be noted that the close proximity of thecomposite layers 34 occurs in three dimensions of a volume of material. - The close proximity of
composite layers 34 and the resultant high energy transfer characteristics of the nanomaterials are determined as a function of the processing times, temperatures and pressures during pyrolysis of tires. -
FIG. 14 depicts an enlarged view of a portion of the electron-microscope scan of the cluster 30-1 9 adjacent to and in close proximity to the cluster 30-1 8 ofFIG. 13 . The composite layers 34 8 and 34 9 of clusters 30-1 8 and 30-1 9 are in close proximity. The cluster 30-1 9 includes, by way of example, nanoclusters 32 9-1, 32 9-2 and 32 9-3. Thenanoclusters composite layer 34 9 by thenanocluster binder 31 9. The zinc sulfide properties of thenanoclusters FIG. 14 ) include many of the materials of TABLE 2 in varying concentrations that are generally less than the concentration of zinc sulfide. The concentration of pyrolitic carbon is typically greater than the concentration of zinc sulfide. The pyrolitic carbon in the composite 34 facilitates the ion formation and charge transport. The other materials of TABLE 2 may also play a contributing role to the operation. -
FIG. 15 depicts an electron-microscope scan showing further details of the nanocluster ofFIG. 14 . -
FIG. 16 depicts an electron-microscope scan showing even further details of the nanocluster ofFIG. 15 . Thenanocluster 32 9-3 is much larger than thenanocluster 32 9-4 and demonstrates that the zinc sulfide nanocluster have widely varying size distributions. - The manufacturing process for forming electrochemical capacitors from tire char, in one embodiment, is as follows. The carbon char from pyrolyzed tires is ground or otherwise formed into a fine powder with a particle size distribution that includes a substantial number of small particles, that is, particles measuring less than 100 nanometers. The resultant fine powder is mixed with an electrolyte solution consisting of approximately 38% NaOH in distilled water at a ratio of 4 g fine powder (carbon) to 3.5 g of electrolyte. This carbon/electrolyte mixture is then ground (if done by hand using a mortar and pestle) for approximately 10 minutes or until the electrode material has a smooth consistency. The ground electrode material can be stored for weeks or more in a sealed container.
- Capacitors are assembled by rolling out the electrode material in a thin layer onto a current collector which, for example, is 316 stainless steel foil supported by a rigid member such as plate glass. A separator is placed atop the thin layer of electrode material. The separator consists of an ion permeable, electrically insulating membrane (Pall Rai membrane) which is pre-saturated with electrolyte solution by soaking in the electrolyte solution for longer than 30 minutes. Another layer of electrode material is placed atop the insulating membrane to form a symmetrical electrode, followed by a collector plate. The capacitor layers are then compressed, for example using clips, sealed with epoxy and allowed to cure at 50° C. for an hour. After the epoxy has cured, the binder clips are removed. The resulting electrochemical capacitors are tested.
- The capacitors are tested by first charging to 0.75V until the current required to maintain this charge level falls below 1 milliamp. The capacitors are then cycled through charge/discharge cycles whereby the charging current is reversed until the potential at the collector reaches 0V. Then the current is switched to charge the capacitors back to their previous potential. The time required to discharge and recharge the cell is recorded as is the current used and the total voltage change. These values along with the carbon mass in each electrode are used to calculate the energy stored in the cell.
- While the invention has been particularly shown and described with reference to preferred embodiments thereof it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention.
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